Discovery of three polymorphs of 7-fluoroisatin reveals challenges in using computational crystal structure prediction as a complement to experimental screening

A combined computational and experimental polymorph search was undertaken to establish the crystal forms of 7-fluoroisatin, a simple molecule with no reported crystal structures, to evaluate the value of crystal structure prediction studies as an aid to solid form discovery. Three polymorphs were found in a manual crystallisation screen, as well as two solvates. Form I ( P2(1)/c, Z0 1), found from the majority of solvent evaporation experiments, corresponded to the most stable form in the computational search of Z0 1 structures. Form III ( P21/ a, Z0 2) is probably a metastable form, which was only found concomitantly with form I, and has the same dimeric R2 2( 8) hydrogen bonding motif as form I and the majority of the computed low energy structures. However, the most thermodynamically stable polymorph, form II ( P1 , Z0 2), has an expanded four molecule R 4 4( 18) hydrogen bonding motif, which could not have been found within the routine computational study. The computed relative energies of the three forms are not in accord with experimental results. Thus, the experimental finding of three crystalline polymorphs of 7- fluoroisatin illustrates the many challenges for computational screening to be a tool for the experimental crystal engineer, in contrast to the results for an analogous investigation of 5- fluoroisatin.

Architect and user interaction: The spoken representation of form and functional meaning

The paper is an investigation of the exchange of ideas and information between an architect and building users in the early stages of the building design process before the design brief or any drawings have been produced. The purpose of the research is to gain insight into the type of information users exchange with architects in early design conversations and to better understand the influence the format of design interactions and interactional behaviours have on the exchange of information. We report an empirical study of pre-briefing conversations in which the overwhelming majority of the exchanges were about the functional or structural attributes of space, discussion that touched on the phenomenological, perceptual and the symbolic meanings of space were rare. We explore the contextual features of meetings and the conversational strategies taken by the architect to prompt the users for information and the influence these had on the information provided. Recommendations are made on the format and structure of pre-briefing conversations and on designers' strategies for raising the level of information provided by the user beyond the functional or structural attributes of space.

Responsiveness to change by standard-form contract drafters: A case study of the FIDIC White Book

Purpose – The purpose of this paper is to focus on the Fédération Internationale des Ingénieurs-Conseils (FIDIC) White Book standard form of building contract. It tracks the changes to this contract over its four editions, and seeks to identify their underlying causes. Design/methodology/approach – The changes made to the White Book are quantified using a specific type of quantitative content analysis. The amended clauses are then examined to understand the nature of the changes made. Findings – The length of the contract increased by 34 per cent between 1990 and 2006. A large proportion of the overall increase can be attributed to the clauses dealing with “conflict of interest/corruption” and “dispute resolution”. In both instances, the FIDIC drafting committees have responded to international developments to discourage corruption, and to encourage the use of alternative dispute resolution. Between 1998 and 2006, the average length of the sentences increased slightly, raising the question of whether long sentences are easily understood by users of contracts. Research limitations/implications – Quantification of text appears to be particularly useful for the analysis of documents which are regularly updated because changes can be clearly identified and the length of sentences can be determined, leading to conclusions about the readability of the text. However, caution is needed because changes of great relevance can be made to contract clauses without actually affecting their length. Practical implications – The paper will be instructive for contract drafters and informative for users of FIDIC's White Book. Originality/value – Quantifying text has been rarely used regarding standard-form contracts in the field of construction.

Recovery of norbixin from a raw extraction solution of annatto pigments using colloidal gas aphrons (CGAs)

Annatto dyes are widely used in food and are finding increasing interest also for their application in the pharmaceutical and cosmetics industry. Bixin is the main pigment extracted from annatto seeds and accounts for 80% of the carotenoids in the outer coat of the seeds; norbixin being the water-soluble form of the bixin. Typically annatto dyes are extracted from the seeds by mechanical means or solutions of alkali, edible oil or organic solvents, or a combination of the two depending on the desired final product. In this work CGAs are investigated as an alternative separation method for the recovery of norbixin from a raw extraction solution of annatto pigments in KOH. A volume of CGAs generated from a cationic surfactant (CTAB) solution is mixed with a volume of annatto solution and when the mixture is allowed to settle it separates into the top aphron phase and the bottom liquid phase. Potassium norbixinate presented in the annatto solution will interact with the surfactant in the aphron phase, which results in the effective separation of norbixin. Recovery= 94% was achieved at a CTAB to norbixin molar ratio of 3.3. In addition a mechanism of separation is proposed here based on the separation results with the cationic surfactant and an anionic surfactant (bis-2-ethyl hexyl sulfosuccinate, AOT) and measurements of surfactant to norbixin ratio in the aphron phase; electrostatic interactions between the surfactant and norbixin molecules result in the fort-nation of a coloured complex and effective separation of norbixin. (c) 2005 Elsevier B.V. All rights reserved.

Treatment response in child anxiety is differentially related to the form of maternal anxiety disorder

An examination was made of the extent to which maternal anxiety predicted response to treatment of children presenting with an anxiety disorder. In a sample of 55 children referred to a local NHS CAMH service for treatment of an anxiety disorder, systematic mental state interview assessment was made of both mothers and children, and both completed self-report questionnaires to assess aspects of anxiety, both immediately before the children received treatment and following treatment. Children of mothers with anxiety disorder overall responded less well to treatment than children of mothers with no anxiety disorder. There was some diagnostic specificity in this in that children of mothers with GAD did as well in treatment as children whose mothers had no anxiety, whereas children of mothers with social phobia did poorly. The outcome for children with anxiety appears to be related to the presence and nature of maternal anxiety. It would seem prudent that treatment of children with anxiety involves assessment of maternal anxiety. It is important to establish in systematic investigation whether treatment of maternal anxiety improves the outcome for child anxiety.

Finding the smallest eigenvalue by the inverse Monte Carlo method with refinement

Finding the smallest eigenvalue of a given square matrix A of order n is computationally very intensive problem. The most popular method for this problem is the Inverse Power Method which uses LU-decomposition and forward and backward solving of the factored system at every iteration step. An alternative to this method is the Resolvent Monte Carlo method which uses representation of the resolvent matrix [I -qA](-m) as a series and then performs Monte Carlo iterations (random walks) on the elements of the matrix. This leads to great savings in computations, but the method has many restrictions and a very slow convergence. In this paper we propose a method that includes fast Monte Carlo procedure for finding the inverse matrix, refinement procedure to improve approximation of the inverse if necessary, and Monte Carlo power iterations to compute the smallest eigenvalue. We provide not only theoretical estimations about accuracy and convergence but also results from numerical tests performed on a number of test matrices.

Finding the point on Bezier Curves with the normal vector passing an external point

Two algorithms for finding the point on non-rational/rational Bezier curves of which the normal vector passes through a given external point are presented. The algorithms are based on Bezier curves generation algorithms of de Casteljau's algorithm for non-rational Bezier curve or Farin's recursion for rational Bezier curve, respectively. Orthogonal projections from the external point are used to guide the directional search used in the proposed iterative algorithms. Using Lyapunov's method, it is shown that each algorithm is able to converge to a local minimum for each case of non-rational/rational Bezier curves. It is also shown that on convergence the distance between the point on curves to the external point reaches a local minimum for both approaches. Illustrative examples are included to demonstrate the effectiveness of the proposed approaches.

Comparison of the computational cost of a Monte Carlo and deterministic algorithm for computing bilinear forms of matrix powers

In this paper we consider bilinear forms of matrix polynomials and show that these polynomials can be used to construct solutions for the problems of solving systems of linear algebraic equations, matrix inversion and finding extremal eigenvalues. An almost Optimal Monte Carlo (MAO) algorithm for computing bilinear forms of matrix polynomials is presented. Results for the computational costs of a balanced algorithm for computing the bilinear form of a matrix power is presented, i.e., an algorithm for which probability and systematic errors are of the same order, and this is compared with the computational cost for a corresponding deterministic method.

Visual motion interferes with lexical decision on motion words

Embodied theories of cognition propose that neural substrates used in experiencing the referent of a word, for example perceiving upward motion, should be engaged in weaker form when that word, for example ‘rise’, is comprehended. Motivated by the finding that the perception of irrelevant background motion at near-threshold, but not supra-threshold, levels interferes with task execution, we assessed whether interference from near-threshold background motion was modulated by its congruence with the meaning of words (semantic content) when participants completed a lexical decision task (deciding if a string of letters is a real word or not). Reaction times for motion words, such as ‘rise’ or ‘fall’, were slower when the direction of visual motion and the ‘motion’ of the word were incongruent — but only when the visual motion was at nearthreshold levels. When motion was supra-threshold, the distribution of error rates, not reaction times, implicated low-level motion processing in the semantic processing of motion words. As the perception of near-threshold signals is not likely to be influenced by strategies, our results support a close contact between semantic information and perceptual systems.